CN106353969B

CN106353969B - Lithographic process and material

Info

Publication number: CN106353969B
Application number: CN201610013802.5A
Authority: CN
Inventors: 郑雅玲; 张庆裕; 王建惟; 陈彦豪
Original assignee: Taiwan Semiconductor Manufacturing Co TSMC Ltd
Current assignee: Taiwan Semiconductor Manufacturing Co TSMC Ltd
Priority date: 2015-07-17
Filing date: 2016-01-08
Publication date: 2020-05-08
Anticipated expiration: 2036-01-08
Also published as: TWI606486B; KR101829961B1; US10394126B2; US20170017158A1; CN111474823B; TWI648596B; KR20170009689A; CN111474823A; TW201705200A; TW201809877A; CN106353969A

Abstract

One of the broader forms of the present invention relates to a method of manufacturing a semiconductor device. The method includes exposing the photoresist layer to a radiation source and applying a hardening agent to the photoresist layer. Thus, after applying the hardener, the first portion of the photoresist layer has a higher glass transition temperature, higher mechanical strength than the second portion of the photoresist layer. Embodiments of the invention relate to lithographic processes and materials.

Description

Lithographic process and material

Technical Field

Embodiments of the invention relate to lithographic processes and materials.

Background

The semiconductor Integrated Circuit (IC) industry has experienced rapid growth over the past several decades. Technological advances in semiconductor materials and design have resulted in increasingly smaller and more complex circuits. These materials and design advances are possible because the technology associated with processing and manufacturing has also experienced technological advances. As the size of the smallest elements decreases, the challenge of reducing pattern collapse, pattern lift-off, and thickness loss increases.

Disclosure of Invention

According to some embodiments of the invention, there is provided a method comprising: exposing the photoresist layer to a radiation source; and applying a hardener to the photoresist layer, wherein after applying the hardener, a first portion of the photoresist layer has a higher glass transition temperature (Tg) or higher mechanical strength than a second portion of the photoresist layer.

According to further embodiments of the present invention, there is also provided a method, including: exposing the photoresist layer to a radiation source; developing the photoresist layer to form a feature; applying a hardener to the component, wherein the hardener increases the glass transition temperature (Tg) of the component or increases the mechanical strength of the component; and applying a smoothing agent to the component, wherein the smoothing agent reduces the glass transition temperature of the component.

There is also provided, in accordance with yet other embodiments of the present invention, material for use in a lithographic process, including: a material having a molecular weight of about 150 daltons to about 3000 daltons, such that the material has one of the following chemical structures:

wherein: r_fRepresents a first spacer group; c represents a group including carbon; ar represents a group including aromatic groups; re represents a second spacer group; p represents a polar group; m represents an integer from 1 to 6; n represents an integer from 1 to 20.

Drawings

Aspects of the invention are best understood from the following detailed description when read with the accompanying drawing figures. It should be noted that, in accordance with standard practice in the industry, various components are not drawn to scale. In fact, the dimensions of the various elements may be arbitrarily increased or decreased for clarity of discussion.

Figure 1 is a diagram illustrating an exemplary photoresist exposure process according to one example of principles described herein.

Fig. 2 is a flow chart of a method for fabricating a semiconductor device in an exemplary embodiment in accordance with aspects of the present invention.

Fig. 3 and 4A are cross-sectional views of a semiconductor device at various stages of manufacture built in accordance with the method of fig. 2.

Fig. 4B, 4C, 4D-4F illustrate a hardener constructed in accordance with some embodiments.

Fig. 5, 6A and 6B are cross-sectional views of a semiconductor device at various stages of manufacture constructed in accordance with the method of fig. 2.

Fig. 7 is a flow chart of a method for fabricating a semiconductor device in an exemplary embodiment in accordance with various aspects of the invention.

Fig. 8A, 8B, 9A, 9B, 9C, and 9D are cross-sectional views of a semiconductor device at various stages of manufacture built in accordance with the method of fig. 7.

Fig. 10A, 10B, 10C, and 10D illustrate a smoothing agent constructed according to some embodiments.

Detailed Description

It is to be understood that the following disclosure provides many different embodiments, or examples, for implementing different features of various embodiments. Specific examples of components and arrangements are described below to simplify the present disclosure. These are, of course, merely examples and are not intended to be limiting. For example, the formation of a first feature over or on a second feature in the description that follows may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments in which additional features may be formed between the first and second features, such that the first and second features may not be in direct contact. In addition, the present invention may repeat reference numerals and/or characters in various embodiments. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.

The invention provides a lithographic method for manufacturing a semiconductor device. The terms lithography, immersion lithography, photolithography and optical lithography are used interchangeably herein. Photolithography is a process used in microfabrication, such as semiconductor fabrication, to selectively remove portions of a thin film or substrate. The process uses light to transfer a pattern (e.g., a geometric pattern) from a photomask to a photosensitive layer (e.g., photoresist, or simply "photoresist") on a substrate. The light causes a chemical change in the exposed areas of the photosensitive layer, which may increase or decrease the solubility of the exposed areas. If the exposed areas become more soluble, the photosensitive layer is referred to as a positive tone photoresist. If the exposed areas become poorly soluble, the photosensitive layer is referred to as a negative photoresist. A baking process, such as a post-exposure baking process, may be performed before or after exposing the substrate. The development process uses a developing solution to selectively remove either the exposed or unexposed regions, thereby creating an exposed pattern over the substrate. A series of chemical processes can then engrave/etch the exposure pattern into the substrate (or material layer) while the patterned photoresist protects the underlying substrate (or material layer) areas. Alternatively, metal deposition, ion implantation, or other processes may be performed. Finally, the appropriate reagents remove (or strip) the remaining photoresist and the substrate is ready to carry out the entire process to be repeated in the next stage of circuit fabrication. In complex integrated circuits (e.g., modern CMOS), the substrate may undergo multiple photolithography cycles.

Fig. 1 is a diagram illustrating an exemplary photoresist exposure process 100. The process 100 includes applying a photoresist layer 120 over the substrate 110. In some embodiments, substrate 110 comprises silicon. Alternatively or additionally, the substrate 110 may include other suitable semiconductor materials, such as germanium (Ge), silicon germanium (SiGe), silicon carbide (SiC), gallium arsenide (GaAs), diamond, indium arsenide (InAs), indium phosphide (InP), silicon germanium carbide (SiGeC), and gallium indium phosphide (GaInP). The substrate 110 may also include various components such as various doped regions, Shallow Trench Isolation (STI) regions, source/drain components, gate stacks, dielectric components, and/or multilevel interconnects.

The photoresist layer 120 is then exposed to a beam of radiation 135 from a source 130 through a photomask (mask or reticle) 140. The photomask 140 has a predetermined pattern. The exposure process will produce a photoresist pattern that includes multiple exposed regions and multiple unexposed regions of the feature, such as an exposure. Fig. 1 shows the photoresist layer 120 in different tones. Region 120A shows the region that is blocked from light source 130, and thus no acid is generated in that region. In contrast, region 120B represents a region that is exposed to light, thereby resulting in an acidogenic chemical reaction within region 120B. The light source 130 may be a variety of light sources, including a Deep Ultraviolet (DUV) light source. In one example, the light source 130 may be an Extreme Ultraviolet (EUV) light source. In some examples, other light sources 130 such as electron beam (e-beam) writing. Alternatively, the exposure process may use other radiation beams such as ion beams, x-rays, and other suitable exposure energies. Additionally, a pre-bake of the photoresist 120 may be performed prior to the exposure process to cure and dry the photoresist 120.

During exposure, when the photoresist layer 120 is a positive tone photoresist, the solubility of the photoresist layer 120 increases (i.e., the acid will cleave the acid cleavable polymer, causing the polymer to become more hydrophilic). Alternatively, when the photoresist layer 120 is a negative tone photoresist, the solubility of the photoresist layer 120 decreases (i.e., the acid will catalyze the acid catalyzed cross-linkable polymer, causing the polymer to become more hydrophobic). Additionally, the photoresist layer 120 may be subjected to a Post Exposure Bake (PEB), and then the photoresist layer 120 is developed by any suitable process to form a pattern in the photoresist layer 120.

Subsequently, a developing solution may be used to remove portions of the photoresist layer 120. Depending on the photoresist type (e.g., positive or negative tone), the developing solution can remove either the exposed portions or the unexposed portions. If the photoresist layer 120 comprises a negative photoresist, the exposed portions are not dissolved by the developing solution and remain over the substrate. If the photoresist layer 120 is a positive tone photoresist, the exposed portions are developed with a positive tone developing solution, leaving unexposed portions. If the photoresist layer 120 is a positive tone photoresist that is developed with a negative tone developing solution, the unexposed portions will dissolve, leaving the exposed portions. The remaining exposed portions (or unexposed portions) define a pattern.

While existing methods of photolithography are generally suitable for their intended purposes, they are not fully satisfactory in all respects. For example, when the photoresist layer 120 includes an alkaline water-soluble component such as a hydroxyl group (e.g., -OH) or a carboxylic acid group (e.g., -COOH), the unexposed pattern portions dissolve when developed by a developer. This problem is called swelling and leads to poor line width variation, film loss and photoresist pattern collision (collision). The present invention provides a photolithography process using a hardening process to reduce poor line width variation, film loss, and photoresist pattern collision.

Fig. 2 illustrates a flow diagram of a method 200 of fabricating a semiconductor device 300, constructed in accordance with some embodiments, in accordance with various aspects of the invention. In various embodiments, the present invention repeats the reference numerals and/or letters. This repetition is for the purpose of simplicity and clarity and so that the repeated reference numerals and/or letters indicate similar elements throughout the various embodiments unless otherwise specified.

Referring to fig. 2, as well as fig. 3, the method 200 begins at step 202 by depositing a photosensitive layer, such as a photoresist layer 120, over the substrate 110, such as using a spin-on technique. The method 200 then proceeds to step 204 where the photoresist layer 120 is exposed to a radiation source. The photoresist layer 120 is exposed to a radiation beam, such as radiation beam 135, from a light source, such as light source 130, through a photomask (mask or reticle) 140 having a predetermined pattern. The exposure process forms a latent pattern in the photoresist layer 120 including a plurality of exposed regions 310 and a plurality of unexposed regions 320. Fig. 3 shows the photoresist layer 120 in a different tone. The darker colored regions 120B represent exposed regions 310 that cause chemical reaction of the acid, while the lighter colored regions 120A show unexposed regions 320 that are blocked from the light source 130 and therefore free of acid. In the exposed regions 310, the radiation beam 135 reaches the photoresist 120 to establish an effective solubility transition between the exposed and

unexposed regions

310 and 320.

After step 204, the method 200 has 2 paths identified by the suffixes "A" and "B", respectively. These 2 paths are discussed separately below. Referring to fig. 2 and 4A, for path a, the method 200 proceeds to step 206A by applying a hardening process using a hardening agent 410 to the photoresist layer 120. The hardening treatment may include a wet treatment using an aqueous solution mixed with the hardening agent 410, which is performed in a wet process table or in a chamber. The concentration of hardener 410 is in the range of about 0.1% to about 50% of the aqueous solution.

During the hardening process, the hardening agent 410 reacts with the top of the photoresist layer 120. Specifically, the hardener reacts with the top of the photoresist layer 120 to increase the surface density, glass transition temperature (Tg), or mechanical strength of the top to form a hardened top layer 120L. Thus, the hardened top layer 120L has a higher glass transition temperature than a second portion of the photoresist layer directly below the hardened top layer 120L.

In one example, hardener 410 has a chemical structure as shown in fig. 4B, including at least a first spacer group R between brackets_f1. A first spacer group R_f1Can include aromatic carbocycle, or straight chain or cycloalkyl with 1-12 carbons in the chain, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, esterEther, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite, or thiol spacer groups. A first spacer group R_f1With polar groups (P)_yWherein y is an integer of at least 2. The polar group P may include-Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR、-OC(O)R*、-C(O)OR*；-C(O)R*；-Si(OR*)₃；-Si(R*)₃(ii) a Epoxy group, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group.

In another example, hardener 410 has another chemical structure shown in fig. 4C, including a first spacer group R between brackets attached to a linking group (L) z_f1Wherein z is an integer of at least 2. The linking group L may comprise-NH₂OH, -SH, -COOH, -COH-COOR, OCOR, COR anhydride, epoxy group, en group, R ' OR, R ' OOR, R ' OSOOR, RX, where R is H, an unbranched OR branched, cyclic OR acyclic, saturated OR unsaturated alkyl OR alkenyl OR alkynyl group. X is halide.

The hardener 410 may also include a surfactant. In some embodiments, the concentration of the surfactant is in the range of about 0.1% to about 10% of the aqueous solution.

Hardener 410 may also include a solvent or aqueous solution. In some embodiments, the concentration of hardener 410 is in the range of about 0.1% to 50% of the solvent.

Specific examples of the hardener 410 may include, but are not limited to, anthracene-1, 8-dicarboxylic acid, di-ethanolamine, and acetone-1, 3-dicarboxylic acid, ethylene diamine, respectively shown in fig. 4D to 4F. Other forms of the stiffening agent 410 may be used according to the principles described herein.

In some embodiments, the polar group (P) of the hardener 410_yAbsorbed by or reacted with developable functional groups (such as-OH or-COOH) on top of the photoresist layer 120 to form a hardened outer layer 120L. In some embodiments, by passing between the hardener 410 and the top of the photoresist layer 120Such as van der waals forces, hydrogen bonds, electronic forces, and ionic forces, form the hardened top layer 120L. For example, when the polar group (P)_yWhen hydroxyl groups are included and the surface of the photoresist layer 120 includes carboxylic acid groups, the hydroxyl units tend to be absorbed by the carboxylic acid groups due to strong hydrogen bonding with each other.

In some embodiments, the hardened top layer 120L is formed by covalent bond formation such as alkylation, condensation, carboxylation, esterification, and/or amidation. For example, when the linking group (L)_zWhen the hydroxyl group is included and the photoresist layer 120 includes the phenol group, the hydroxyl group tends to react with the phenol group to form a covalent bond between the hardener 410 and the outer layer of the photoresist layer 120.

Referring to fig. 2 and also to fig. 5, the method 200 proceeds along path a to step 208A by developing the photoresist layer 120 with the hardened top layer 120L to form a photoresist feature 510. A developing solution may be used to remove portions of the photoresist layer 120. An example of a developing solution is tetramethylammonium hydroxide (TMAH). Any concentration level of TMAH developer solution, such as about 2.38% TMAH developer solution, may be used. Depending on the type of photoresist, the developing solution may remove either the exposed portions or the unexposed portions. For example, if the photoresist layer 120 comprises a negative photoresist, the exposed portions are not dissolved by the developing solution and remain over the substrate 110. If the photoresist layer 120 comprises a positive photoresist, the exposed portions are dissolved by the developing solution, leaving unexposed portions. The semiconductor device 300 may then be subjected to a rinsing process such as a Deionized (DI) water rinse. The rinsing process may remove residual particles. Additionally, a Post Exposure Bake (PEB) is performed prior to developing the photoresist layer 120.

During the development process, the hardened top layer 120L slows down the attack of the photoresist layer 120 by a developer (such as TMAH). Since the hardened top layer 120L slows the development of the photoresist layer 120, less film loss and less line width variation occurs during the formation of the photoresist feature 510.

As described above, after step 204, the method 200 has 2 paths identified by the suffixes "a" and "B", respectively. Turning now to path B, and referring to fig. 2 and 6A-6B, the method 200 proceeds to step 206B by developing the photoresist layer 120 using an in situ hardening process with a hardening agent 410 to form a photoresist feature 510. The in situ hardening process may include introducing the hardening agent 410 into the developing solution, such as by mixing. That is, under path B, the hardener 410 is not separately applied before developing the photoresist layer 120. In contrast, the hardener 410 is part of the developing solution applied to the photoresist layer 420.

During the development process, the hardening agent 410 is absorbed by the photoresist layer 120 and/or reacts with the photoresist layer 120, which is similar in many respects to those discussed above with respect to fig. 4A. The hardener 410 has a multi-polar group P, and the hardener 410 is absorbed by and/or reacted with a functional group (e.g., -OH or-COOH) in a top layer of the photoresist layer 120. The hardener 410 slows down the attack of the developer solution (such as TMAH) on the photoresist layer 120 by making the surface of the photoresist layer 120 have a lower affinity for the developer. It results in an increase in the mechanical strength of the photoresist member 510, thereby mitigating collapse of the photoresist member 510.

Additional steps may be performed before, during, and after the method 200, and some of the steps described above may be replaced or eliminated with respect to other embodiments of the method 200. For example, for path a, a curing process is performed after step 206A and before step 208A. The curing process may include Ultraviolet (UV) curing, plasma curing, radiation curing, baking, or any suitable process.

Fig. 7 is a flow chart of an exemplary method 1000 of another photolithographic process for fabricating the semiconductor device 300. The present disclosure repeats reference numerals and/or letters in the various embodiments. This repetition is for the purpose of simplicity and clarity and so that the repeated reference numbers and/or letters indicate similar elements in the various embodiments unless otherwise specified. Method 1000 begins with

steps

1002 and 1004, which steps 1002 and 1004 are similar to

steps

202 and 204 of method 200. For simplicity and clarity, the above description of step 202 and step 204 applies to step 1002 and step 1004, respectively, and is not repeated here.

Next, referring to fig. 7 and 8A, the method 1000 proceeds to step 1006 by developing the photoresist layer 120 to form a photoresist feature 1200. The development process is similar in many respects to those discussed above with respect to fig. 5. As discussed above, the photoresist layer 120 typically contains some basic water-soluble groups such as hydroxyl groups (e.g., -OH) or carboxylic acid groups (e.g., -COOH). These basic water-soluble groups sometimes cause the unexposed portions of the pattern to be partially dissolved by (or swollen by) the developer during the development process. This unintended partial dissolution (or swelling) of the unexposed portions of the photoresist layer 120 results in the photoresist feature 1200 having an undulating profile/sidewall 1200S, as shown in fig. 8B. The present invention provides a method that can reduce the extent of the wavy profile of the photoresist member 1200 using an adjustable smoothing process.

Referring to fig. 7 and 9A-9B, the method 1000 proceeds to step 1008 by applying an adjustable smoothing process to the photoresist member 1200 to reduce the extent of the wavy profile. The adjustable smoothing process includes applying a hardener 410 and a smoothing agent 1300 to the photoresist component 1200. In the present embodiment, the smoothing agent 1300 is selected to lower the glass transition temperature (Tg) of the photoresist layer 120 to soften the photoresist layer 120. This softening process smoothes the sidewall profile 1200S. Meanwhile, the hardener 410 increases the glass transition temperature (Tg) or mechanical strength of the photoresist layer 120 to harden the photoresist layer 120 to prevent the photoresist member 1200 from collapsing.

Considering the characteristics of the photoresist feature 1200, such as critical dimensions and aspect ratio, an appropriate balance of the smoothing agent 1300 and the hardening agent 410 is selected to achieve a degree of reduction of the wavy sidewall profile to produce a smooth profile 1200T without collapse of the photoresist feature 1200, as shown in fig. 9B. In this embodiment, the molecular weight of the smoothing agent 1300 ranges from 150 daltons to 3000 daltons.

In some embodiments, as shown in fig. 9A, the hardener 410 and the smoothing agent 1300 are applied to the photoresist component 1200 simultaneously, such as by mixing the hardener 410 and the smoothing agent 1300 simultaneously. The hardener 410 tends to adsorb on the photoresist layer 120 first due to its more polar functional group P, which has a higher affinity to the surface of the photoresist layer 120. In some embodiments, the hardener 410 and the smoothing agent 1300 are applied separately so that the hardener 410 is first applied to the photoresist member 1200, and the smoothing agent 1300 is applied next, as shown in fig. 9C to 9D. Then, during the adjustable smoothing process, both the hardener 410 and the smoothing agent 1300 are removed in situ.

The smoothing agent 1300 has the general structure shown in FIG. 10A, which includes a second spacer group R_f2Said R is_f2And a group (C) including carbon between parentheses_mAnd (4) connecting. A second spacer group R_f2Having an aromatic carbocyclic ring, or a linear or cycloalkyl/alkoxy/fluoroalkyl fluoroalkoxy chain having 1-4 carbons in the chain, or a linear or cyclic olefin, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite, or thiol spacer group having 1-4 carbons in the chain, -Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)_2、-SO₂R*、SOR、-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃And epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group. Where m and n are 2 integers. In some embodiments, m is from 1 to 6 and n is from 1 to 20.

Referring again to FIG. 10A, the group comprising carbon (C)_mTo the reactive group Re. The reactive group Re comprises H, OH, a halide, or an aromatic carbocycle, or a linear or cyclic alkyl, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite, or thiol spacer group having 1-12 carbons in the chain.

A second spacer group R_f2And the reactive group Re may also contain-Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR、-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃And epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group.

The smoothing agent 1300 can have another chemical structure shown in FIG. 10B, which includes a second spacer group R_f2Said R is_f2With Ar including aromatic groups between parentheses. The Ar group may include unsaturated hydrocarbons having a carbon number ranging from 2 to 16. The Ar group is attached to the reactive group Re.

The smoothing agent 1300 may also have another chemical structure shown in FIG. 10C, which includes a second spacer group R_f2Said R is_f2And a group (C) including carbon between parentheses_mAnd a reactive group Re. The reactive group Re between brackets is coupled with a polar group P. Group comprising carbon (C)_mTo 2 further reactive groups Re.

The smoothing agent 1300 may also have another chemical structure shown in FIG. 10D, which includes a second spacer group R_f2Said R is_f2Attached to the Ar group and the reactive group Re between brackets. The reactive group Re between brackets is attached to 2 polar groups P. The Ar group is linked to 2 further reactive groups Re. Additional steps may be performed before, during, and after method 1000, and some of the above steps may be replaced or eliminated with respect to other embodiments of method 1000. For example, after step 1008, a curing process is applied to the photoresist component 1200 to enhance the smoothing effect. The curing process may include Ultraviolet (UV) curing, plasma curing, radiation curing, baking, or any suitable process. For example, after step 1008, another step in the method 1000 may include performing a second development process and for enhancing the smoothing effect.

Based on the foregoing, the present invention provides a method for photolithography processing. The method employs applying a hardening process to the photoresist layer and applying an adjustable smoothing process to the photoresist features. The method exhibits reduced LWR, photoresist feature collapse, and film loss. The adjustable smoothing process achieves a smooth sidewall profile of the photoresist features while enhancing the photoresist mechanical performance.

The present invention relates to a method of manufacturing a semiconductor device. The method includes exposing the photoresist layer to a radiation source and applying a hardening agent to the photoresist layer. Thus, after applying the hardener, the first portion of the photoresist layer has a higher glass transition temperature, or a higher mechanical strength, than the second portion of the photoresist layer.

Another method of manufacturing a semiconductor device includes exposing a photoresist layer to a radiation source, developing the photoresist layer to form a part, applying a hardening agent to the part, wherein the hardening agent increases the glass transition temperature of the part and applying a smoothing agent to the part, wherein the smoothing agent decreases the glass transition temperature of the part.

Materials used in photolithographic processes include materials having molecular weights in the range of about 150 daltons to about 3000 daltons. The material comprises a spacer group R_fA group comprising carbon and a reactive group, or a spacer group R_fIncluding aromatic and reactive groups, or spacer groups R_fA group comprising carbon, a polar group and a reactive group, or a spacer group R_fIncluding aromatic groups, polar groups, and reactive groups.

In the above method, further comprising developing the photoresist layer after applying the hardener to the photoresist layer.

In the above method, applying the hardener to the photoresist layer comprises: developing the photoresist layer while applying the hardening agent.

In the above method, the hardener is mixed in the developing solution.

In the above method, the first portion comprises a top of the photoresist layer and the second portion comprises a bottom of the photoresist layer, the bottom being disposed directly below the top of the photoresist layer.

In the above method, the hardener comprises a chemical structure of:

R_f-(P)_y

wherein R is_fRepresents a spacer group, P represents a polar group, y represents an integer of at least 2, wherein R represents_fSelected from the group consisting of aromatic carbocycles, or straight or cyclic alkyl, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, and nitrite or thiol spacer groups having 1 to 12 carbons in the chain; wherein P is selected from the group consisting of-Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*；-SR、-SO₂N(R*)₂、-SO₂R*、SOR、-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃Preferably NHR1R2, R1/R2 comprises H or an alkyl, alkyne, alkyl, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile and nitrite.

In the above method, the hardener comprises a chemical structure of:

R_f-(L)_zwherein R is_fRepresents a spacer group; l represents a linking group; z represents an integer of at least 2; wherein, R is_fSelected from aromatic carbocycle or straight chain or cycloalkyl with 1-12 carbons in the chain, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide and nitrateNitrile, nitrite or thiol spacer groups; and wherein L is selected from the group consisting of-NH₂-OH, -SH, -COOH, -COH, -COOR, OCOR, COR anhydride, epoxy group, en group, R ' OR, R ' OOR, R ' OSOOR, RX, where R is H, an unbranched OR branched, cyclic OR acyclic saturated OR unsaturated alkyl OR alkenyl OR alkynyl group, and X is a halide.

In the above method, the hardener is selected from the group consisting of anthracene-1, 8-dicarboxylic acid, di-ethanolamine and acetone-1, 3-dicarboxylic acid, ethylene diamine.

In the above method, the part has a first cross-sectional profile shape before the application of the smoothing agent and the hardening agent, and wherein the part has a second cross-sectional profile shape after the application of the smoothing agent and the hardening agent, the second cross-sectional profile shape being different from the first cross-sectional profile shape.

In the above method, after the application of the hardener and the leveler, the Tg of the part produced is lowered.

In the above method, the hardener is applied before the smoothing agent is applied to the part.

In the above method, the hardening agent and the smoothing agent are simultaneously applied to the part.

In the above method, the smoothing agent comprises a chemical structure of:

wherein R is_fRepresents a first spacer group, CRepresents a group comprising carbon, Re represents a second spacer group, m represents an integer from 1 to 6, n represents an integer from 1 to 20, wherein R represents_fSelected from the group consisting of aromatic carbocycles, or linear or cycloalkyl/alkoxy/fluoroalkyl fluoroalkoxy chains having 1-4 carbons in the chain, or linear or cyclic olefins having 1-4 carbons in the chain, alkynes, hydroxyls, ketones, aldehydes, carbonates, carboxylic acids, esters, ethers, amides, amines, imines, imides, azides, nitrates, nitriles, nitrites, or thiol spacers, -Cl, -Br, -I; -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR、-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃Epoxy groups, wherein R is H, an unbranched or branched, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group, where x and y are 2 integers; wherein Re is selected from H, OH, halide, or aromatic carbocycle, or straight chain or cycloalkyl with 1-12 carbons in the chain, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite, or thiol spacer, -Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*,-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR；-OC(O)R*、-C(O)OR*、-C(O)R*,-Si(OR*)₃、-Si(R*)₃And epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group.

In the above method, the smoothing agent comprises a chemical structure of:

wherein R is_fRepresents a first spacer group, Ar represents a group comprising an aromatic group, Re represents a second spacer group, n represents from 1 to 20An integer wherein R is_fSelected from the group consisting of aromatic carbocycles, or linear or cycloalkyl/alkoxy/fluoroalkyl fluoroalkoxy chains having 1-4 carbons in the chain, or linear or cyclic olefins having 1-4 carbons in the chain, alkynes, hydroxyls, ketones, aldehydes, carbonates, carboxylic acids, esters, ethers, amides, amines, imines, imides, azides, nitrates, nitriles, nitrites, or thiol spacers, -Cl, -Br, -I; -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR、-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃Epoxy groups, wherein R is H, an unbranched or branched, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group, where x and y are 2 integers; wherein the Ar group comprises an unsaturated hydrocarbon having a carbon number in the range of from 2 to 16; wherein Re is selected from H, OH, halide, or aromatic carbocycle, or straight chain or cycloalkyl with 1-12 carbons in the chain, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite, or thiol spacer, -Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO2N(R*)₂、-SO₂R*、SOR；-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃And epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group.

In the above method, the smoothing agent comprises a chemical structure of:

wherein R is_fRepresents a first spacer group; c represents a group including carbon; re represents a second spacer group; p represents a polar group; m represents an integer of from 1 to 6(ii) a n represents an integer from 1 to 20; wherein, R is_fSelected from the group consisting of aromatic carbocycles, or linear or cycloalkyl/alkoxy/fluoroalkyl fluoroalkoxy chains having 1-4 carbons in the chain, or linear or cyclic olefins having 1-4 carbons in the chain, alkynes, hydroxyls, ketones, aldehydes, carbonates, carboxylic acids, esters, ethers, amides, amines, imines, imides, azides, nitrates, nitriles, nitrites, or thiol spacers, -Cl, -Br, -I; -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR、-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃Epoxy groups, wherein R is H, an unbranched or branched, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group, where x and y are 2 integers; wherein Re is selected from H, OH, halide, or aromatic carbocycle, or straight chain or cycloalkyl with 1-12 carbons in the chain, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite, or thiol spacer, -Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO2N(R*)₂、-SO₂R*、SOR、-OC(O)R*、-C(O)OR*、-C(O)R*,-Si(OR*)₃、-Si(R*)₃Epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group; and wherein P is selected from the group consisting of-Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR；-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃And epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group.

In the above method, the smoothing agent comprises a chemical structure of:

wherein R is_fRepresents a first spacer group; ar represents a group including aromatic groups; re represents a second spacer group; p represents a polar group; n represents an integer from 1 to 20; wherein, R is_fSelected from aromatic carbocycle or straight chain or cycloalkyl/alkoxy/fluoroalkyl fluoroalkoxy chain with 1-4 carbons in the chain, or straight chain or cycloolefine with 1-4 carbons in the chain, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite or thiol spacer group, -Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN；-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR,-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃Epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group; wherein the Ar group comprises an unsaturated hydrocarbon having a carbon number in the range of from 2 to 16; and wherein Re is selected from the group consisting of H, OH, halide, or aromatic carbocycle, or a linear or cyclic alkyl, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite, or thiol spacer having 1-12 carbons in the chain, -Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR；-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃Epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group; and wherein P is selected from the group consisting of-Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR；-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃And epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group.

In the above method, the smoothing agent has a molecular weight in the range of about 150 daltons to about 3000 daltons.

In the above materials, R is_fSelected from aromatic carbocycle or straight chain or cycloalkyl/alkoxy/fluoroalkyl fluoroalkoxy chain with 1-4 carbons in the chain, or straight chain or cycloolefine with 1-4 carbons in the chain, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite or thiol spacer group, -Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN；-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR,-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃And epoxy group, wherein R is H, orA branched or branched, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group; the Ar group comprises an unsaturated hydrocarbon having a carbon number in the range of from 2 to 16; the Re is selected from H, OH, halide, aromatic carbocycle or straight chain or naphthenic base with 1-12 carbons in the chain, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite or thiol spacer group, -Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR；-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃Epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group; and said P is selected from the group consisting of-Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR；-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃And epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group.

Components of several embodiments are discussed above. Those skilled in the art should appreciate that they may readily use the present disclosure as a basis for designing or modifying other processes and structures for carrying out the same purposes and/or achieving the same advantages of the embodiments introduced herein. Those skilled in the art should also realize that such equivalent constructions do not depart from the spirit and scope of the present disclosure, and that they may make various changes, substitutions and alterations herein without departing from the spirit and scope of the present disclosure.

Claims

1. A method for lithography, comprising:

exposing the photoresist layer to a radiation source; and

developing the photoresist layer to form a patterned photoresist layer, wherein the developing comprises applying a developing solution comprising a hardener, and wherein the developing produces a first portion of the photoresist layer having a higher glass transition temperature (Tg) or higher mechanical strength than a second portion of the photoresist layer;

applying a smoothing agent to the patterned photoresist layer, wherein the smoothing agent reduces the glass transition temperature of the patterned photoresist layer.

2. The method of claim 1, wherein the first portion comprises a top of the photoresist layer and the second portion comprises a bottom of the photoresist layer, the bottom being disposed directly below the top of the photoresist layer.

3. The method of claim 1, wherein the hardener comprises a chemical structure of:

R_f-(P)_y

wherein R is_fRepresents a spacer group, and is a cyclic or cyclic alkyl group,

p represents a polar group, and P represents a polar group,

y represents an integer of at least 2,

wherein R is_fSelected from the group consisting of aromatic carbocycles, or straight or cyclic alkyl, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, and nitrite or thiol spacer groups having 1 to 12 carbons in the chain;

wherein P is selected from the group consisting of-Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*；-SR、-SO₂N(R*)₂、-SO₂R*、SOR、-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃Wherein R is H, an unbranched or branched chain, a cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group, wherein the alkyl or alkenyl or alkynyl group is a cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl groupThe hardener is NHR1R2, R1/R2 includes H or alkyl, alkyne, alkyl, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, and nitrite.

4. The method of claim 2, wherein the hardener comprises a chemical structure of:

R_f-(L)_Z

wherein R is_fRepresents a spacer group;

l represents a linking group;

z represents an integer of at least 2;

wherein, R is_fSelected from the group consisting of aromatic carbocycles, or straight or cyclic alkyl, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite, or thiol spacer groups having 1 to 12 carbons in the chain; and

wherein L is selected from the group consisting of-NH₂-OH, -SH, -COOH, -COH, -COOR, OCOR, COR anhydride, epoxy group, en group, R ' OR, R ' OOR, R ' OSOOR, RX, where R is H, an unbranched OR branched, cyclic OR acyclic saturated OR unsaturated alkyl OR alkenyl OR alkynyl group, and X is a halide.

5. The method of claim 2, the hardener being selected from the group consisting of anthracene-1, 8-dicarboxylic acid, di-ethanolamine and acetone-1, 3-dicarboxylic acid, ethylene diamine.

6. A method for lithography, comprising:

exposing the photoresist layer to a radiation source;

developing the photoresist layer to form a feature;

applying a hardener to the component, wherein the hardener increases the glass transition temperature (Tg) of the component or increases the mechanical strength of the component; and

applying a smoothing agent to the component, wherein the smoothing agent reduces the glass transition temperature of the component.

7. The method of claim 6, wherein the part has a first cross-sectional profile shape prior to applying the smoothing agent and the hardening agent, and

wherein after applying the smoothing agent and the hardening agent, the part has a second cross-sectional profile shape that is different from the first cross-sectional profile shape.

8. The method of claim 6, wherein the resulting glass transition temperature of the part is reduced after applying the hardener and the leveler.

9. The method of claim 7, wherein the hardener is applied prior to applying the smoothing agent to the part.

10. The method of claim 7, wherein the hardening agent and the smoothing agent are applied to the component simultaneously.

11. The method of claim 6, wherein the smoothing agent comprises a chemical structure of:

wherein R is_fRepresents a first spacer group, and is a second spacer group,

c represents a group including carbon,

re represents a second spacer group, and Re represents a second spacer group,

m represents an integer of from 1 to 6,

n represents an integer from 1 to 20,

wherein, R is_fSelected from aromatic carbocyclic rings, or rings in a chainA linear or cycloalkyl/alkoxy/fluoroalkyl fluoroalkoxy chain having 1 to 4 carbons, or a linear or cycloalkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite, or thiol spacer group, -Cl, -Br, -I having 1 to 4 carbons in the chain; -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR、-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃Epoxy groups, wherein R is H, an unbranched or branched, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group, where x and y are 2 integers;

wherein Re is selected from H, OH, halide, or aromatic carbocycle, or straight chain or cycloalkyl with 1-12 carbons in the chain, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite, or thiol spacer, -Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*,-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR；-OC(O)R*、-C(O)OR*、-C(O)R*,-Si(OR*)₃、-Si(R*)₃And epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group.

12. The method of claim 6, wherein the smoothing agent comprises a chemical structure of:

wherein R is_fRepresents a first spacer group, and is a second spacer group,

ar represents a group including an aromatic group,

re represents a second spacer group, and Re represents a second spacer group,

n represents an integer from 1 to 20,

wherein, R is_fSelected from the group consisting of aromatic carbocycles, or linear or cycloalkyl/alkoxy/fluoroalkyl fluoroalkoxy chains having 1-4 carbons in the chain, or linear or cyclic olefins having 1-4 carbons in the chain, alkynes, hydroxyls, ketones, aldehydes, carbonates, carboxylic acids, esters, ethers, amides, amines, imines, imides, azides, nitrates, nitriles, nitrites, or thiol spacers, -Cl, -Br, -I; -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR、-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃Epoxy groups, wherein R is H, an unbranched or branched, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group, where x and y are 2 integers;

wherein the Ar group comprises an unsaturated hydrocarbon having a carbon number in the range of from 2 to 16;

wherein Re is selected from H, OH, halide, or aromatic carbocycle, or straight chain or cycloalkyl with 1-12 carbons in the chain, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite, or thiol spacer, -Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO2N(R*)₂、-SO₂R*、SOR；-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃And epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group.

13. The method of claim 6, wherein the smoothing agent comprises a chemical structure of:

wherein R is_fRepresents a first spacer group;

c represents a group including carbon;

re represents a second spacer group;

p represents a polar group;

m represents an integer from 1 to 6;

n represents an integer from 1 to 20;

wherein Re is selected from H, OH, halide, or aromatic carbocycle, or straight chain or cycloalkyl with 1-12 carbons in the chain, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite, or thiol spacer, -Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO2N(R*)₂、-SO₂R*、SOR、-OC(O)R*、-C(O)OR*、-C(O)R*,-Si(OR*)₃、-Si(R*)₃Epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group; and

wherein P is selected from the group consisting of-Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR；-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃And epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group.

14. The method of claim 6, wherein the smoothing agent comprises a chemical structure of:

wherein R is_fRepresents a first spacer group;

ar represents a group including aromatic groups;

re represents a second spacer group;

p represents a polar group;

n represents an integer from 1 to 20;

wherein, R is_fSelected from aromatic carbocycle or straight chain or cycloalkyl/alkoxy/fluoroalkyl fluoroalkoxy chain with 1-4 carbons in the chain, or straight chain or cycloolefine with 1-4 carbons in the chain, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite or thiol spacer group, -Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN；-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR,-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃Epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group;

wherein the Ar group comprises an unsaturated hydrocarbon having a carbon number in the range of from 2 to 16; and

wherein Re is selected from H, OH, halide, or aromatic carbocycle, or straight chain or cycloalkyl with 1-12 carbons in the chain, alkoxy, fluoroalkyl, fluoroalkoxy, alkene, alkyne, hydroxyl, ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine, imine, imide, azide, nitrate, nitrile, nitrite, or thiol spacer, -Cl, -Br, -I, -NO₂、-SO₃-、-H-、-CN、-NCO、-OCN、-CO₂-、-OH、-OR*、-OC(O)CR*、-SR、-SO₂N(R*)₂、-SO₂R*、SOR；-OC(O)R*、-C(O)OR*、-C(O)R*、-Si(OR*)₃、-Si(R*)₃Epoxy groups, wherein R is H, an unbranched or branched chain, cyclic or acyclic saturated or unsaturated alkyl or alkenyl or alkynyl group; and

15. The method of claim 6, wherein the smoothing agent has a molecular weight in the range of 150 daltons to 3000 daltons.